JP4155923B2 - Honeycomb structure and manufacturing method thereof - Google Patents

Honeycomb structure and manufacturing method thereof Download PDF

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JP4155923B2
JP4155923B2 JP2003534361A JP2003534361A JP4155923B2 JP 4155923 B2 JP4155923 B2 JP 4155923B2 JP 2003534361 A JP2003534361 A JP 2003534361A JP 2003534361 A JP2003534361 A JP 2003534361A JP 4155923 B2 JP4155923 B2 JP 4155923B2
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honeycomb
adhesive
spacer
honeycomb structure
thickness
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JPWO2003031371A1 (en
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純 藤田
幸久 和田
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NGK Insulators Ltd
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NGK Insulators Ltd
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    • B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
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    • B32—LAYERED PRODUCTS
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Description

技術分野
本発明は、内燃機関、ボイラー、化学反応機器及び燃料電池用改質器等の触媒作用を利用する触媒用担体又は排ガス中の微粒子捕集フィルター等に用いられるハニカム構造体及びその製造方法に関し、特に寸法精度に優れ、接着部のクラックなどの不良の発生しにくいハニカム構造体及びその製造方法に関する。
背景技術
内燃機関、ボイラー、化学反応機器及び燃料電池用改質器等の触媒作用を利用する触媒用担体又は俳ガス中の微粒子、特にディーゼル微粒子の捕集フィルター等にハニカム構造体が用いられている。
この様な目的で使用されるハニカム構造体は、排気ガスの急激な温度変化や局所的な発熱によってハニカム構造内の温度分布が不均一となり、構造体にクラックを生ずる等の問題があった。特にディーゼルエンジンの排気中の粒子状物質を捕集するフィルター（以下ＤＰＦという）として用いられる場合には、たまったカーボン微粒子を燃焼させて除去し再生することが必要であり、この際に局所的な高温化が避けられないため、大きな熱応力が発生し易く、クラックが発生し易かった。
このため、ハニカム構造体を複数に分割したセグメントを接合材により接合する方法が提案された。例えば、米国特許第４３３５７８３号公報には、多数のハニカム体を不連続な接合材で接合するハニカム構造体の製造方法が開示されている。また、特公昭６１−５１２４０号公報には、セラミック材料よりなるハニカム構造のマトリックスセグメントを押出し成形し、焼成後その外周部を加工して平滑にした後、その接合部に焼成後の鉱物組成がマトリックスセグメントと実質的に同じで、かつ熱膨脹率の差が８００℃において０．１％以下となるセラミック接合材を塗布し、焼成する耐熱衝撃性回転蓄熱式が提案されている。また、１９８６年のＳＡＥ論文８６０００８には、コージェライトのハニカムセグメントを同じくコージェライトセメントで接合したセラミックハニカム構造体が開示されている。更に特開平８−２８２４６号公報には、ハニカムセラミック部材を少なくとも三次元的に交錯する無機繊維、無機バインダー、有機バインダー及び無機粒子からなる弾性質シール材で接着したセラミックハニカム構造体が開示されている。
しかしながら、ハニカム構造体は、一般に金属製の缶体等で囲繞して使用されるが、ハニカム構造体を上述のように分割した場合、分割されたセグメントを一体化し金属製の缶体などに囲繞する必要がある。この際、上述のような従来の接着方法で一体化されたハニカム構造体は、接着層の厚さが不均一となるため、充分な寸法精度を得ることができず、寸法不良や接着部のクラックの原因ともなっていた。
発明の開示
本発明は、この様な事情に鑑みてなされたものであり、その目的とするところは、ハニカムセグメント間の接着層の厚さを所望の厚さとし、かつ均一の厚さとすることにより、ハニカム構造体の接着層の厚さの寸法不良が少ないハニカム構造体及びその製造方法を提供することにある。
本発明は、隔壁により仕切られた軸方向に貫通する多数の流通孔を有する複数のハニカムセグメントが一体化されてなるハニカム構造体であって、前記ハニカムセグメント間にスペーサーが配置されていることを特徴とするハニカム構造体を提供するものである。本発明において、スペーサーが、無機物又は有機物から選ばれた１種又は２種以上であることが好ましく、更にスペーサーの厚さが０．１〜３．０ｍｍであることが好ましい。
本発明は、また、隔壁により仕切られた軸方向に貫通する多数の流通孔を有するハニカムセグメントを製造する工程、及び複数の前記ハニカムセグメントを接着一体化する工程を備えるハニカム構造体の製造方法であって、前記ハニカムセグメントを接着一体化する工程において、スペーサーを接着面に介在させることを特徴とするハニカム構造体の製造方法を提供するものである。本発明において、スペーサーが無機物又は有機物から選ばれた１種又は２種以上であることが好ましく、更にスペーサーの厚さが、０．１〜３．０ｍｍであることが好ましい。また、ハニカムセグメントを接着一体化する工程が、ハニカムセグメントの接着面にスペーサーを形成する工程、ハニカムセグメントの接着面に接着剤を施与する工程、及びハニカムセグメントを接着する工程を含むことが好ましく、更に、スペーサーをハニカムセグメントの接着面に形成する工程が、接着面上に流動性のスペーサー形成剤を配置し、これを固化させることにより行われることが好ましい。更に、接着剤の主成分と、スペーサー形成剤の主成分が、同一であることが好ましい。
発明を実施するための最良の形態
以下、図面にしたがって、本発明のハニカム構造体及びその製造方法の内容を詳細に説明するが、本発明は以下の実施形態に限定されるものではない。なお、以下において断面とは、特に断りのない限り流通孔の長手方向に対する垂直の断面を意味する。
本発明のハニカム構造体１は、例えば図１（ａ）及び（ｂ）に示すように、Ｘ軸方向に貫通する多数の流通孔３を有するハニカム構造からなる複数のハニカムセグメント１２が一体化されてなるものである。
本発明の重要な特徴は、図２に示すようにハニカムセグメント間にスペーサー１０が配置されていることである。この様にスペーサー１０が配置されることにより、１つの接着面７の面上において、接着層８の厚さを所望の厚さとすることができ、かつ１つの接着面７における接着層８の厚さのばらつきも少なくなり、良好な寸法精度のハニカム構造体１とすることができる。この様なハニカム構造体１は、接着層の高温挙動が安定し、これを金属などの缶体で囲繞する際にハニカムセグメント間の寸法の違いによる応力集中が起きにくくなるため、接着部におけるハニカム構造体のクラックが発生しにくくなることも期待できる。
本発明において、スペーサー１０は、接着層８の厚さを所定の厚さに保つことができる形状であれば特に形状に制限はなく、例えば断面が一定の厚さを有する板状体のほか、断面が例えば凹凸を有するなど一定の厚さを有していなくても、例えば接着の際に凸部が所定の厚さとなるものなど、接着層の厚さを所定の厚さに保つことができるものであればよい。スペーサー１０の厚さに特に制限はないが、厚すぎると接着層が厚くなりすぎ、ハニカム構造体の圧力損失が大きくなり、薄すぎると本発明の効果が得られにくくなり好ましくない。スペーサー１０の厚さは、好ましくは０．１〜３．０ｍｍ、更に好ましくは０．２〜１．５ｍｍ、最も好ましくは０．３〜０．８ｍｍである。ここで、スペーサー１０の厚さとは、スペーサー１０に凹凸がある場合は、凸部の厚さ、すなわち２つのハニカムセグメントを一定距離に保つことのできる部分の厚さをいう。スペーサー１０の平面形状にも特に制限はなく、図３に示すような四角形状のほか、三角形、その他の多角形状、円形、楕円形状などあらゆる形状をとることができる。スペーサー１０の大きさや数も特に制限はなく、接着面７の大きさに合わせて適宜選択することができる。スペーサー１０の接着面７における設置位置にも特に制限はなく、好ましくはスペーサー１０の大きさや数に合わせて、接着面全体に均等に適宜設置することができる。
スペーサー１０の材質に特に制限はなく、例えばボール紙や、木材、プラスチック、ゴム等の有機物、ハニカム構造体やセラミック接着材と同材質のもや、その他のセラミックスを含めた無機物、金属などを用いることができる。また、スペーサーとして使用される材料は、ハニカム構造体が使用時に高温に晒されることを考慮すれば、有機物と金属は、高温で燃焼もしくは融解もしくは蒸発することによって、ハニカム構造体とセラミック接着材の欠陥や高温物性に影響しないものが好ましく、無機物はハニカム構造体とセラミック接着材の一方もしくは両方に近い材料組成や高温物性、例えば熱膨張率、熱伝導率などを持つものがハニカム構造体とセラミック接着材の欠陥や高温物性に影響しないので好ましく、更に好ましくはセラミック接着材と同材質のものが、接合後にセラミック接着材と同化するため好ましい。即ち、後述する接着材とスペーサーの材料としての性質が同様のものが好ましく、従って、接着材を構成する成分とスペーサーを構成する成分の５０質量％以上が同一であることが好ましく、さらには７０質量％以上、特に９０質量％以上が同一であることが好ましく、実質的にすべて同一であることが最も好ましい。
本発明において、接着層８は、一般的にスペーサー１０とともに接着材９を含み、この接着材９によりハニカムセグメント１２同士が接着されている。接着材の種類に特に制限はなく、ハニカムセグメントの材質に合った公知の接着材を用いることができるが、例えばセラミックファイバー等の無機繊維、セラミック粉等の無機粉体及び有機・無機のバインダー等を混合した接着剤などから形成されたセラミック接着材等が好ましい。更に、Ｓｉゾルなどのゾル状物質を含む接着剤から形成されることも好ましい。また、複数の種類の接着材を用いてもよく、この場合に、接着層を複数の層とすることも好ましい。この様に接着層を複数の層とする場合には、例えばハニカムセグメントと接する接着層の組成をハニカムセグメントの組成に近いものとし、傾斜的に接着層の組成を変化させることも好ましい。ここで、接着材とは、接着層を構成する物質を意味し、接着剤とは接着材を形成する材料を意味する。従って、一般には、接着剤が何らかの変化、例えば乾燥等による成分比の変化や化学変化、をして接着材となるが、接着剤と接着材が同一の場合もありうる。
本発明において、接着層８の厚さに特に制限はないが、接着層８の厚さが厚すぎるとハニカム構造体の排気ガス通過時の圧力損失が大きくなりすぎ、薄すぎると接着剤が本来の接着機能を有しなくなる場合があり好ましくない。接着層８の好ましい厚さの範囲は、０．１〜３．０ｍｍ、更に好ましくは０．３〜２．０ｍｍ、特に好ましくは０．５〜１．５ｍｍである。
本発明において、ハニカムセグメント１２は強度、耐熱性等の観点から、主成分が、炭化珪素、窒化珪素、コージェライト、アルミナ、ムライト、ジルコニア、燐酸ジルコニウム、アルミニウムチタネート、チタニア及びこれらの組み合わせよりなる群から選ばれる少なくとも１種のセラミックス、Ｆｅ−Ｃｒ−Ａｌ系金属、ニッケル系金属又は金属ＳｉとＳｉＣとからなることが好ましい。ここで、主成分とは成分の８０質量％以上を占め、主結晶相となるものを意味する。
また、本発明において、ハニカムセグメント１２が金属ＳｉとＳｉＣからなる場合、Ｓｉ／（Ｓｉ＋ＳｉＣ）で規定されるＳｉ含有量が５〜５０質量％であることが好ましく、１０〜４０質量％であることが更に好ましい。５質量％未満ではＳｉ添加の効果が得られにくく、５０質量％を超えるとＳｉＣの特徴である耐熱性、高熱伝導性の効果が得られにくいからである。この場合に、接着材９も金属ＳｉかＳｉＣの一方もしくは両方からなるものを含むことが好ましい。
本発明において、ハニカムセグメント１２のセル密度（単位断面積当たりの流通孔３の数）は、特に制限はないが、セル密度が小さすぎると、幾何学的表面積が不足し、大きすぎると圧力損失が大きくなりすぎるため好ましくない。セル密度は、０．９〜３１０セル／ｃｍ２（６〜２０００セル／平方インチ）であることが好ましい。また、流通孔３の断面形状（セル形状）は、特に制限はなく、三角形、四角形及び六角形等の多角形状、円形、楕円形状、コルゲート形状などのあらゆる形状をとることができるが、製作上の観点から、三角形、四角形及び六角形ののうちのいずれかであることが好ましい。また、隔壁２の厚さにも特に制限はないが、隔壁の厚さが薄すぎるとハニカムセグメントとしての強度が不足し、厚すぎると圧力損失が大きくなりすぎ好ましくない。隔壁２の厚さは５０〜２０００μｍの範囲であることが好ましい。
また、ハニカムセグメント１２の形状に特に制限はなくあらゆる形状をとることができるが、例えば図３に示すような四角柱状を基本形状として、これを図１（ａ）及び（ｂ）に示すように接着一体化させ、ハニカム構造体１の最外周面を構成するハニカムセグメントの形状をハニカム構造体１の外周形状に合わせることが好ましい。また、各ハニカムセグメント１２を扇形状の断面形状とすることもできる。
本発明のハニカム構造体１の断面形状に特に制限はなく、図１（ａ）及び（ｂ）に示す円形のほか、楕円形、長円形等、図２に示す四角形のほか、三角形、五角形等の多角形、及び無定形状等あらゆる形状をとることができる。本発明のハニカム構造体を触媒担体として、内燃機関、ボイラー、化学反応機器、燃料電池用改質器等に用いる場合、ハニカム構造体が触媒能を有する金属を担持していることも好ましい。触媒能を有する代表的なものとしてはＰｔ、Ｐｄ、Ｒｈ等が挙げられ、これらのうちの少なくとも１種をハニカム構造体が担持していることが好ましい。
一方、本発明のハニカム構造体をＤＰＦのような、排気ガス中に含まれる粒子状物質を捕集除去するためのフィルターとして用いる場合、ハニカム構造体の流通孔３の開口部が交互に目封止されていることが好ましい。流通孔３の開口部が交互に目封止されていることにより、ハニカム構造体の一端面より粒子状物質を含んだ排気ガスを通すと、排気ガスは当該一端面側の開口部が目封止されていない流通孔３よりハニカム構造体１の内部に流入し、濾過能を有する多孔質の隔壁２を通過し、他の端面側の開口部が目封止されていない流通孔３より排出される。この隔壁を通過する際に粒子状物質が隔壁に捕捉される。なお、捕捉された粒子状物質が隔壁上に堆積してくると、圧損が急激に上昇し、エンジンに負荷がかかり、燃費、ドライバビリティが低下するので、定期的にヒーター等の加熱手段により、粒子状物質を燃焼除去し、フィルター機能を再生させるようにする。この燃焼再生時、燃焼を促進させるため、ハニカム構造体が上述のような触媒能を有する金属を担持していてもよい。
つぎに、本発明のハニカム構造体の製造方法について説明する。
本発明のハニカム構造体の製造方法において、まず、ハニカムセグメント１２を製造する。ハニカムセグメント１２の製造工程に特に制限はなく、一般的にハニカム構造を有するものを製造する方法を用いることができるが、例えば次のような工程で製造することができる。
原料として、例えば炭化珪素、窒化珪素、コージェライト、アルミナ、ムライト、ジルコニア、燐酸ジルコニウム、アルミニウムチタネート、チタニア及びこれらの組み合わせよりなる群から選ばれる少なくとも１種のセラミックス、Ｆｅ−Ｃｒ−Ａｌ系金属、ニッケル系金属又は金属ＳｉとＳｉＣ等を用い、これにメチルセルロース及びヒドロキシプロポキシルメチルセルロース等のバインダー、界面活性剤及び水等を添加して、可塑性の坏土を作製する。
この坏土を、例えば押出成形し、隔壁２により仕切られた軸方向に貫通する多数の流通孔３を有する形状のハニカム成形体を成形する。
これを、例えばマイクロ波及び熱風などで乾燥した後、焼成することにより、図３に示すようなハニカムセグメント１２を製造することができる。ここで製造するハニカムセグメント１２は、上述のハニカム構造体の発明の説明において述べた好ましい形状とすることができる。
本発明において、ハニカムセグメント１２を製造した後、これらのハニカムセグメントを接着一体化する。
この工程は、図４（ａ）及び（ｂ）に示すように２つの接着面７の少なくとも一方に接着剤を施与し及び／又はスペーサー１０の少なくとも１つの面に接着剤を施与し、スペーサー１０を２つの接着面の間に介在させた状態で２つの接着面７を接着する。この際、接着するハニカムセグメント１２を押圧して接着することが簡便で良好な接着力を得ることができるため好ましい。
この工程で用いる接着剤は、上述のハニカム構造体の発明において述べた接着層８に含まれる好ましい接着材９を形成する接着剤であることが好ましく、この場合に、接着層を複数の層とするように２以上の異なる組成の接着剤を２度以上に分けて施与することも好ましい。この様に接着層を複数の層とする場合には、例えばハニカムセグメントと接する接着層の組成がハニカムセグメントの組成に近いものとなるような接着剤を用い、傾斜的に接着層の組成が変化するような接着剤を用いることも好ましい。また、接着剤の種類によっては、更に乾燥及び／又は焼成することによりより強固な接着力を得ることができる。
ハニカムセグメントを接着一体化する別の好ましい方法は、例えば図７に示すように、ハニカムセグメント１２の接着面７上に、スペーサー１０を形成する工程と、図８に示すように接着面７に接着剤１３を施与する工程と、図９に示すように、２以上のハニカムセグメント１２を接着する工程を含む方法である。
スペーサー１０を形成する工程は、接着面７上にスペーサーを固着する工程であり、例えば、スペーサー形成剤を、スペーサーを形成すべき所定の位置に所定量配置し、加熱や乾燥することによりスペーサーを接着面７上に固着することができる。スペーサー形成剤は流動性であることが好ましく、流動性のスペーサー形成剤を所定位置に配置した後、固化させて接着面上に固着することが好ましい。スペーサー形成剤を所定位置に配置する方法としては、例えば、一定量だけ排出することができるポンプを用いて、接着面上の所定位置に所定量配置する方法が好ましい。配置されたスペーサー形成剤を接着面７上に固着してスペーサーを形成する方法としては、スペーサー形成材料を加熱や乾燥することにより固着する方法が好ましく、このためには、一般に用いられる種々の加熱装置、乾燥装置、加熱・乾燥装置を用いることができる。ここで、スペーサーが所定の厚さとなるように、スペーサー形成剤を加圧しながら加熱及び／又は乾燥することが好ましい。
スペーサーを接着面上で固化させて、接着面上に固着する方法の一例として図１０にホットプレート１６を用いた例を示した。図１０において、所定厚み、例えば０．５ｍｍ厚みの板１５をホットプレート１６上に配設し、スペーサー形成剤１７が配置された接着面の、スペーサー形成剤が配置された部分以外の部分をその板１５上に接触させることにより、スペーサー形成剤１７が０．５ｍｍの厚みのスペーサーとなるようにホットプレートにより加圧しながら加熱する。この場合、ハニカムセグメントの自重、又は上下を逆にした場合にはホットプレートの自重により加圧してもよく、また、加圧装置を用いて加圧してもよい。このような方法により、所定厚みのスペーサーをばらつきなく形成することができる。
スペーサー形成剤としては、セラミックスを含むスラリーが好ましく、更にハニカムセグメントの構成成分と共通の成分を含むことが好ましい。例えば、ハニカムセグメントの構成成分と共通のセラミックス粉に、セラミックファイバー等の無機繊維、有機・無機のバインダー及び水などの分散媒を添加ししたものなどが好ましく、更にＳｉゾルなどのゾル状物質を含むことも好ましい。
スペーサー形成剤は、接着層を挟んで対向することとなる２つの接着面の何れかに配置すればよいが、両方に配置してもよい。スペーサー形成剤の量、配置位置、配置数に特に制限はなく、上述のような方法で所望の厚さとなる程度の量を接着層の厚みが均一となるように適宜バランスよく配置することができる。なお、場合により、スペーサー形成剤を配置する前に、接着面に下地剤をスプレーなどで塗布してもよい。下地剤を塗布することにより、スペーサーを接着面との接着強度を向上させることができる。但し、下地剤は、ハニカムセグメント同士を接着するものではない。
接着剤を接着面に施与する工程は、上述と同様、接着面の何れか一方又は両方に接着剤を施与することにより行われる。この場合に、スペーサーが形成された接着面に施与しても、スペーサーが形成されていない接着面に施与しても、両方に施与してもよい。接着剤は、スペーサー形成剤と同様にセラミックスを含むスラリーが好ましく、例えば、ハニカムセグメントの構成成分と共通のセラミックス粉に、セラミックファイバー等の無機繊維、有機・無機のバインダー及び水などの分散媒を添加ししたものなどが好ましく、更にＳｉゾルなどのゾル状物質を含むことも好ましい。また、接着剤の主成分とスペーサー形成剤の主成分とが同一であること、すなわち、接着剤の構成成分とスペーサー形成剤の構成成分の５０質量％以上が同一の成分であることが好ましい。但し、粒子径等の形状が異なっていてもよい。更に７０質量％以上、特に９０質量％以上が同一の成分であることが、接着性を高め、欠陥を作りにくくする観点から好ましい。更に、形成される接着材及びスペーサーの構成成分が実質的に同一となるような接着剤とスペーサー形成剤であることが好ましい。
このようにスペーサーが形成され、接着剤が施与された２以上のハニカムセグメントを上述と同様に、好ましくは押圧しながら接着し、好ましくは乾燥及び／又は加熱することにより、２以上のハニカムセグメントを接着一体化することができ、ハニカム構造体を製造することができる。この際の押圧力に得に制限はないが、０．３〜３ｋｇｆ／ｃｍ２程度の圧力で押圧することが好ましく、更に０．５〜２ｋｇｆ／ｃｍ２程度の圧力で押圧することが好ましい。
このような方法で、ハニカム構造体を製造することにより、スペーサーの位置ずれを抑制することができる。また、スペーサー及び接着材をセラミックスとし、主成分を同一とした場合に、予めスペーサーを作成しておく必要がなく、上記工程を一連の工程として自動化が可能であり、量産に好適に対応できるという利点も有する。
また、本発明により製造されたハニカム構造体１をフィルター、特にＤＰＦ等に用いる場合には、流通孔３の開口部を封止材により交互に目封止することが好ましく、更に端面を交互に千鳥模様状になるように目封止することが好ましい。封止材による目封止は、目封止をしない流通孔をマスキングし、原料をスラリー状として、ハニカムセグメントの開口端面に施与し、乾燥後焼成することにより行うことができる。この場合は、上述のハニカムセグメントの製造工程の間、すなわちハニカムセグメントの成形後、焼成前に目封止すると焼成工程が１回で済むため好ましいが、焼成後に目封止してもよく、成形後であればどの時点で行ってもよい。用いる目封止材の材料は、前述のハニカムセグメントの好ましい原料として挙げた群の中から好適に選ぶことができるが、ハニカムセグメントに用いる原料と同じ原料を用いることが好ましい。
また、本発明において、ハニカム構造体に触媒を担持させてもよい。この方法は、当業者が通常行う方法でよく、例えば触媒スラリーをウォッシュコートして乾燥、焼成することにより触媒を担持させることができる。この工程もハニカムセグメントの成形後であればどの時点で行ってもよい。
以下、本発明を実施例により具体的に説明するが、本発明はこれら実施例に何ら限定されるものではない。
（実施例及び比較例）
つぎに、実施例に基づき、本発明を更に詳しく説明する。
（ハニカムセグメントの製造）
原料として、炭化珪素粉末と珪素粉末を使用し、これにメチルセルロース及びヒドロキシプロポキシルメチルセルロース、界面活性剤及び水を添加して、可塑性の坏土を作製した。この坏土を押出成形し、マイクロ波及び熱風で乾燥した。つぎに、これを大気雰囲気中で加熱脱脂し焼成して、寸法が５８ｍｍ×５８ｍｍ×１５０ｍｍ（高さ）の図３に示すような四角柱状ハニカムセグメントを得た。
（実施例１）
上記製造工程で得られた、ハニカムセグメントを２つ、スペーサーとして寸法が５０ｍｍ×１０ｍｍ×０．８ｍｍ（厚さ）のボール紙を２辺、及びＳｉＣ４０質量％、シリカゾル２０質量％、無機助剤１質量％、セラミックファイバー３０質量％、水９質量％で構成されるセラミックス製接着剤を用意し、図４（ａ）及び（ｂ）に示すように、ハニカムセグメントの側面、すなわち接着面にセラミック製接着剤を施与し、ボール紙を該側面の上下２箇所に配置し、押圧接着して乾燥することにより、２つのハニカムセグメントが一体化されたハニカム構造体を得た。
（比較例１）
スペーサーであるボール紙を用いなかったことを除いて、実施例１と同様の操作を行い、ハニカム構造体を得た。
（接着層の厚さの測定）
実施例１及び比較例１で得られた各々のハニカム構造体について、図６の接着面７において、丸で囲った１〜１０の数字で示した１０箇所の測定点１１における接着層の厚さを測定した。測定結果を表１に示す。

Figure 0004155923
実施例１で得られたハニカム構造体は、スペーサーであるボール紙を介在させることにより、接着層の厚さを、ほぼボール紙の厚さ、すなわち所望の厚さとすることができた。また、測定点間のばらつきも非常に少なく接着層の厚さを一定に保つことができた。
（実施例２）
上記製造工程で得られた、ハニカムセグメントを２つ、スペーサーとして寸法が１０ｍｍ×１０ｍｍ×０．８ｍｍ（厚さ）でＳｉＣ４３質量％、シリカゾル２３質量％、無機助剤２質量％、セラミックファイバー３２質量％、で構成される無機材料を４辺、及び接着剤としてＳｉＣ４０質量％、シリカゾル２０質量％、無機助剤１質量％、セラミックファイバー３０質量％、水９質量％で構成されるセラミックス製接着剤を用意し、図５（ａ）及び（ｂ）に示すように、ハニカムセグメントの側面、すなわち接着面にセラミック製接着剤を施与し、無機材料を該側面の上下４箇所に配置し、押圧接着して乾燥させることにより、２つのハニカムセグメントが一体化されたハニカム構造体を得た。
（比較例２）
スペーサーである無機材料を用いなかったことを除いて、実施例２と同様の操作を行い、ハニカム構造体を得た。
（接着層の厚さの測定）
実施例２及び比較例２で得られた各々のハニカム構造体について、図６の接着面７において、丸で囲った１〜１０の数字で示した１０箇所の測定点１１における接着層の厚さを測定した。測定結果を表２に示す。
Figure 0004155923
実施例２で得られたハニカム構造体は、スペーサーである無機材料を介在させることにより、接着層の厚さを、ほぼ無機材料の厚さ、すなわち所望の厚さとすることができた。また、測定点間のばらつきも非常に少なく接着層の厚さを一定に保つことができた。
（実施例３）
上記ハニカムセグメントの製造で得られたハニカムセグメント２０個を用意し、実施例２で用いた接着剤をスペーサー形成剤として、定量供給ポンプを用いて、接着面の４隅近傍の４箇所に配置した後、図１０に示すように、厚さ０．５ｍｍの鉄板を配設したホットプレート上に置き、約１６０℃で約６秒間加熱して固化させて、図７に示すように、ハニカムセグメントの接着面上に固着された４個のスペーサーを形成した。このスペーサーの厚みを測定したところ、０．５±０．１ｍｍの範囲に収まった。
つぎに、スペーサーが形成されたハニカムセグメントの面に、スペーサー形成剤と同一のものを接着剤として、図８に示すように所定量施与した後、４列×４列の合計１６個のハニカムセグメントを一体化するよう接着面同士を接着し、１．０ｋｇｆ／ｃｍ２の加圧力で押圧した。つぎに、接着面からはみ出した接着剤を除去し、乾燥してハニカム構造体を得た。
（比較例３）
スペーサーである無機材料を用いなかったことを除いて、実施例３と同様の操作を行い、ハニカム構造体を得た。
（接着層の厚さの測定）
実施例３及び比較例３で得られた各々のハニカム構造体について、図６の接着面７において、丸で囲った１〜１０の数字で示した１０箇所の測定点１１における接着層の厚さを測定した。測定結果を表３に示す。実施例３で得られたハニカム構造体は、スペーサーである無機材料を介在させることにより、測定点間のばらつきも少なく接着層の厚さを所定の厚さに一定に保つことができた。
Figure 0004155923
産業上の利用可能性
本発明のハニカム構造体は、ハニカムセグメント間にスペーサーが配置されているため、ハニカムセグメント間の接着層の厚さを所望の厚さとし、かつ均一にすることができ、これにより寸法精度の不良が少ないハニカム構造体を得ることができた。また、本発明の製造方法により、上記のような効果を有するハニカム構造体を容易に作ることができた。本発明のハニカム構造体は、内燃機関、ボイラー、化学反応機器及び燃料電池用改質器等の触媒作用を利用する触媒用担体又は排ガス中の微粒子捕集フィルター等に好適に用いることができる。
【図面の簡単な説明】
図１（ａ）及び（ｂ）は、本発明に係るハニカム構造体の一形態を示す模式図であり、図１（ａ）は斜視図、図１（ｂ）は平面模式図である。
図２は、本発明に係る構造体のほかの形態を示す模式的な断面図である。
図３は、本発明に係るハニカムセグメントの一形態を示す模式的な斜視図である。
図４（ａ）及び（ｂ）は、本発明に係るハニカムセグメントにスペーサーを配置した模式図であり、図４（ａ）は側面図、図４（ｂ）は正面図である。
図５（ａ）及び（ｂ）は、本発明に係るハニカムセグメントにスペーサーを配置した別の模式図であり、図５（ａ）は側面図、図５（ｂ）は正面図である。
図６は、実施例１〜３において製造されたハニカムセグメントの側面図に接着層の厚さの測定点を示した説明図である。
図７は、本発明の製造方法の一例を示す図であり、ハニカムセグメントの接着面にスペーサーを形成した状態を示す模式的な斜視図である。
図８は、本発明の製造方法の一例を示す図であり、ハニカムセグメントの接着面に接着剤を施与した状態を示す模式的な斜視図である。
図９は、本発明の製造方法の一例を示す図であり、ハニカムセグメントを接着一体化した状態を示す模式的な斜視図である。
図１０は、本発明の製造方法の一例を示す図であり、ハニカムセグメントの接着面に配置されたスペーサー形成剤を加熱している状態を示す模式的な斜視図である。Technical field
The present invention relates to a honeycomb structure used for a catalyst carrier utilizing a catalytic action of an internal combustion engine, a boiler, a chemical reaction device, a fuel cell reformer, or the like, or a particulate collection filter in exhaust gas, and a manufacturing method thereof, In particular, the present invention relates to a honeycomb structure excellent in dimensional accuracy and less likely to cause defects such as cracks in an adhesive portion, and a method for manufacturing the same.
Background art
Honeycomb structures are used for catalyst carriers that utilize the catalytic action of internal combustion engines, boilers, chemical reaction devices, fuel cell reformers, and the like, or filters for collecting particulates in haiku gas, particularly diesel particulates.
The honeycomb structure used for such a purpose has a problem that the temperature distribution in the honeycomb structure becomes non-uniform due to a rapid temperature change of the exhaust gas or local heat generation, and the structure is cracked. In particular, when used as a filter (hereinafter referred to as DPF) for collecting particulate matter in diesel engine exhaust, it is necessary to burn off, remove, and regenerate the accumulated carbon particles. Therefore, large heat stress is apt to occur and cracks are likely to occur.
For this reason, a method of joining segments obtained by dividing a honeycomb structure into a plurality of pieces with a joining material has been proposed. For example, US Pat. No. 4,335,783 discloses a method for manufacturing a honeycomb structure in which a large number of honeycomb bodies are joined with discontinuous joining materials. In Japanese Patent Publication No. 61-51240, a honeycomb structured matrix segment made of a ceramic material is extruded, and after firing, the outer peripheral portion thereof is processed and smoothed, and then the joint has a mineral composition after firing. A thermal shock-resistant rotational heat storage method has been proposed in which a ceramic bonding material that is substantially the same as the matrix segment and has a thermal expansion coefficient difference of 0.1% or less at 800 ° C. is applied and fired. Also, SAE paper 860008 of 1986 discloses a ceramic honeycomb structure in which honeycomb segments of cordierite are joined with cordierite cement. Further, JP-A-8-28246 discloses a ceramic honeycomb structure in which honeycomb ceramic members are bonded with an elastic sealing material composed of inorganic fibers, inorganic binders, organic binders, and inorganic particles that cross at least three-dimensionally. Yes.
However, the honeycomb structure is generally used by being surrounded by a metal can body or the like, but when the honeycomb structure is divided as described above, the divided segments are integrated into a metal can body or the like. There is a need to. At this time, the honeycomb structure integrated by the conventional bonding method as described above has a non-uniform thickness of the bonding layer, so that sufficient dimensional accuracy cannot be obtained. It was also a cause of cracks.
Disclosure of the invention
The present invention has been made in view of such circumstances, and the object of the present invention is to make the thickness of the adhesive layer between the honeycomb segments a desired thickness and a uniform thickness, thereby achieving a honeycomb structure. It is an object of the present invention to provide a honeycomb structure having a small dimensional defect in the thickness of the adhesive layer of the body and a method for manufacturing the honeycomb structure.
The present invention is a honeycomb structure in which a plurality of honeycomb segments having a large number of flow holes penetrating in the axial direction partitioned by partition walls are integrated, and spacers are disposed between the honeycomb segments. A featured honeycomb structure is provided. In the present invention, the spacer is preferably one or more selected from inorganic or organic substances, and the spacer preferably has a thickness of 0.1 to 3.0 mm.
The present invention is also a method for manufacturing a honeycomb structure including a step of manufacturing a honeycomb segment having a large number of flow holes penetrating in the axial direction partitioned by partition walls, and a step of bonding and integrating the plurality of honeycomb segments. Then, in the step of bonding and integrating the honeycomb segments, a method for manufacturing a honeycomb structure is provided, wherein a spacer is interposed on the bonding surface. In the present invention, the spacer is preferably one or more selected from inorganic or organic substances, and the spacer preferably has a thickness of 0.1 to 3.0 mm. Preferably, the step of bonding and integrating the honeycomb segments includes a step of forming a spacer on the bonding surface of the honeycomb segment, a step of applying an adhesive to the bonding surface of the honeycomb segment, and a step of bonding the honeycomb segment. Furthermore, it is preferable that the step of forming the spacer on the bonding surface of the honeycomb segment is performed by disposing a fluid spacer forming agent on the bonding surface and solidifying it. Furthermore, the main component of the adhesive and the main component of the spacer forming agent are preferably the same.
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the contents of the honeycomb structure of the present invention and the manufacturing method thereof will be described in detail with reference to the drawings. However, the present invention is not limited to the following embodiments. In the following, the cross section means a cross section perpendicular to the longitudinal direction of the flow hole unless otherwise specified.
In the honeycomb structure 1 of the present invention, for example, as shown in FIGS. 1A and 1B, a plurality of honeycomb segments 12 having a honeycomb structure having a large number of flow holes 3 penetrating in the X-axis direction are integrated. It will be.
An important feature of the present invention is that spacers 10 are arranged between the honeycomb segments as shown in FIG. By arranging the spacer 10 in this way, the thickness of the adhesive layer 8 can be set to a desired thickness on the surface of one adhesive surface 7, and the thickness of the adhesive layer 8 on one adhesive surface 7. The variation in thickness is reduced, and the honeycomb structure 1 with good dimensional accuracy can be obtained. In such a honeycomb structure 1, the high-temperature behavior of the adhesive layer is stable, and stress concentration due to the difference in dimensions between the honeycomb segments is less likely to occur when the adhesive layer is surrounded by a can such as a metal. It can also be expected that cracks in the structure are less likely to occur.
In the present invention, the spacer 10 is not particularly limited in shape as long as the thickness of the adhesive layer 8 can be maintained at a predetermined thickness. For example, in addition to a plate-like body having a constant cross section, Even if the cross section does not have a certain thickness such as unevenness, the thickness of the adhesive layer can be kept at a predetermined thickness, for example, the convex portion has a predetermined thickness during bonding. Anything is acceptable. The thickness of the spacer 10 is not particularly limited, but if it is too thick, the adhesive layer becomes too thick, the pressure loss of the honeycomb structure increases, and if it is too thin, the effects of the present invention are not easily obtained. The thickness of the spacer 10 is preferably 0.1 to 3.0 mm, more preferably 0.2 to 1.5 mm, and most preferably 0.3 to 0.8 mm. Here, the thickness of the spacer 10 means the thickness of the convex portion, that is, the thickness of the portion that can keep the two honeycomb segments at a constant distance when the spacer 10 has irregularities. The planar shape of the spacer 10 is not particularly limited, and may be any shape such as a triangular shape, other polygonal shapes, a circular shape, an elliptical shape in addition to a rectangular shape as shown in FIG. The size and number of the spacers 10 are not particularly limited and can be appropriately selected according to the size of the bonding surface 7. There is no particular limitation on the installation position of the spacer 10 on the bonding surface 7. Preferably, the spacer 10 can be appropriately and uniformly installed on the entire bonding surface according to the size and number of the spacers 10.
The material of the spacer 10 is not particularly limited, and for example, cardboard, organic materials such as wood, plastic, rubber, the same material as the honeycomb structure or ceramic adhesive, other inorganic materials including ceramics, metal, etc. are used. be able to. Also, considering that the material used as the spacer is exposed to high temperatures during use, the organic substance and the metal are burned, melted or evaporated at high temperatures, so that the honeycomb structure and the ceramic adhesive Those that do not affect defects and high-temperature physical properties are preferable, and inorganic materials have a material composition and high-temperature physical properties close to one or both of the honeycomb structure and ceramic adhesive, such as those having a honeycomb structure and ceramics. This is preferable because it does not affect the defects of the adhesive and the high-temperature physical properties. More preferably, the same material as the ceramic adhesive is preferable because it is assimilated with the ceramic adhesive after joining. That is, it is preferable that the properties of the adhesive and the spacer, which will be described later, are the same. Therefore, it is preferable that 50% by mass or more of the component constituting the adhesive and the component constituting the spacer are the same, and 70 It is preferable that the mass% or more, particularly 90 mass% or more is the same, and it is most preferable that substantially all are the same.
In the present invention, the adhesive layer 8 generally includes an adhesive 9 together with the spacer 10, and the honeycomb segments 12 are bonded to each other by the adhesive 9. There are no particular restrictions on the type of adhesive, and known adhesives suitable for the material of the honeycomb segment can be used. For example, inorganic fibers such as ceramic fibers, inorganic powders such as ceramic powder, and organic and inorganic binders A ceramic adhesive or the like formed from an adhesive mixed with or the like is preferable. Furthermore, it is also preferable to form from an adhesive containing a sol-like substance such as Si sol. In addition, a plurality of types of adhesive materials may be used, and in this case, the adhesive layer is preferably a plurality of layers. When the adhesive layer is made into a plurality of layers as described above, it is preferable that the composition of the adhesive layer in contact with the honeycomb segment is close to the composition of the honeycomb segment and the composition of the adhesive layer is changed in an inclined manner. Here, the adhesive means a substance constituting the adhesive layer, and the adhesive means a material forming the adhesive. Therefore, in general, the adhesive is subjected to some change, for example, a change in component ratio or chemical change due to drying or the like, and becomes an adhesive. However, the adhesive and the adhesive may be the same.
In the present invention, the thickness of the adhesive layer 8 is not particularly limited. However, if the thickness of the adhesive layer 8 is too thick, the pressure loss when the honeycomb structure passes through the exhaust gas becomes too large. It is not preferable because the adhesive function may not be provided. The preferable thickness range of the adhesive layer 8 is 0.1 to 3.0 mm, more preferably 0.3 to 2.0 mm, and particularly preferably 0.5 to 1.5 mm.
In the present invention, the honeycomb segment 12 is composed of silicon carbide, silicon nitride, cordierite, alumina, mullite, zirconia, zirconium phosphate, aluminum titanate, titania, and combinations thereof from the viewpoint of strength, heat resistance, and the like. It is preferable to consist of at least one ceramic selected from the group consisting of Fe—Cr—Al-based metal, nickel-based metal, or metal Si and SiC. Here, a main component means what occupies 80 mass% or more of a component, and becomes a main crystal phase.
In the present invention, when the honeycomb segment 12 is made of metal Si and SiC, the Si content defined by Si / (Si + SiC) is preferably 5 to 50% by mass, and 10 to 40% by mass. Is more preferable. If the amount is less than 5% by mass, the effect of Si addition is difficult to obtain, and if it exceeds 50% by mass, the effects of heat resistance and high thermal conductivity, which are the characteristics of SiC, are difficult to obtain. In this case, it is preferable that the adhesive 9 also includes one made of one or both of metal Si and SiC.
In the present invention, the cell density (the number of flow holes 3 per unit cross-sectional area) of the honeycomb segment 12 is not particularly limited, but if the cell density is too small, the geometric surface area is insufficient, and if it is too large, the pressure loss Is not preferable because it becomes too large. Cell density is 0.9-310 cells / cm 2 (6 to 2000 cells / square inch) is preferable. The cross-sectional shape (cell shape) of the flow hole 3 is not particularly limited, and can be any shape such as a polygon, such as a triangle, a quadrangle, and a hexagon, a circle, an ellipse, and a corrugated shape. In view of the above, it is preferably any one of a triangle, a square, and a hexagon. Further, the thickness of the partition wall 2 is not particularly limited, but if the partition wall thickness is too thin, the strength as the honeycomb segment is insufficient, and if it is too thick, the pressure loss becomes too large, which is not preferable. The thickness of the partition wall 2 is preferably in the range of 50 to 2000 μm.
The shape of the honeycomb segment 12 is not particularly limited and can be any shape. For example, a rectangular column shape as shown in FIG. 3 is used as a basic shape, as shown in FIGS. 1 (a) and 1 (b). It is preferable that the shape of the honeycomb segment constituting the outermost peripheral surface of the honeycomb structure 1 is matched with the outer peripheral shape of the honeycomb structure 1 by bonding and integrating. Each honeycomb segment 12 may have a fan-shaped cross-sectional shape.
The cross-sectional shape of the honeycomb structure 1 of the present invention is not particularly limited. Besides the circular shape shown in FIGS. 1A and 1B, an elliptical shape, an oval shape, etc. In addition to the square shape shown in FIG. 2, a triangular shape, a pentagonal shape, etc. Any shape such as a polygon and an indefinite shape can be taken. When the honeycomb structure of the present invention is used as a catalyst carrier in an internal combustion engine, a boiler, a chemical reaction device, a fuel cell reformer, or the like, it is also preferable that the honeycomb structure supports a metal having catalytic ability. Typical examples of catalytic ability include Pt, Pd, Rh and the like, and it is preferable that at least one of these is supported by the honeycomb structure.
On the other hand, when the honeycomb structure of the present invention is used as a filter for collecting and removing particulate matter contained in exhaust gas such as DPF, the openings of the flow holes 3 of the honeycomb structure are alternately plugged. It is preferably stopped. Since the openings of the flow holes 3 are alternately plugged, when exhaust gas containing particulate matter is passed from one end face of the honeycomb structure, the exhaust gas is plugged in the opening on the one end face side. It flows into the inside of the honeycomb structure 1 from the flow holes 3 that are not stopped, passes through the porous partition walls 2 having filtration ability, and is discharged from the flow holes 3 in which the opening on the other end face side is not plugged. Is done. Particulate matter is trapped in the partition as it passes through the partition. In addition, if the trapped particulate matter accumulates on the partition wall, the pressure loss increases rapidly, the engine is loaded, and fuel consumption and drivability are reduced. The particulate matter is burned and removed to regenerate the filter function. In order to promote combustion at the time of this combustion regeneration, the honeycomb structure may carry a metal having the above catalytic ability.
Next, a method for manufacturing the honeycomb structure of the present invention will be described.
In the method for manufacturing a honeycomb structure of the present invention, first, the honeycomb segment 12 is manufactured. The manufacturing process of the honeycomb segment 12 is not particularly limited, and generally a method for manufacturing a honeycomb segment 12 can be used. For example, the honeycomb segment 12 can be manufactured by the following process.
As a raw material, for example, at least one ceramic selected from the group consisting of silicon carbide, silicon nitride, cordierite, alumina, mullite, zirconia, zirconium phosphate, aluminum titanate, titania and combinations thereof, Fe—Cr—Al-based metal, A nickel-based metal or metal Si and SiC are used, and a binder such as methyl cellulose and hydroxypropoxyl methyl cellulose, a surfactant, water, and the like are added thereto to produce a plastic clay.
The kneaded material is extruded, for example, to form a honeycomb formed body having a large number of flow holes 3 penetrating in the axial direction partitioned by the partition walls 2.
The honeycomb segment 12 as shown in FIG. 3 can be manufactured by drying this with, for example, microwaves and hot air, and then firing. The honeycomb segment 12 manufactured here can have a preferable shape described in the description of the invention of the honeycomb structure.
In the present invention, after the honeycomb segments 12 are manufactured, these honeycomb segments are bonded and integrated.
This step involves applying an adhesive to at least one of the two adhesive surfaces 7 and / or applying an adhesive to at least one surface of the spacer 10 as shown in FIGS. 4 (a) and (b), The two bonding surfaces 7 are bonded together with the spacer 10 interposed between the two bonding surfaces. At this time, it is preferable to press and bond the honeycomb segments 12 to be bonded, because a simple and good bonding force can be obtained.
The adhesive used in this step is preferably an adhesive that forms a preferable adhesive 9 included in the adhesive layer 8 described in the invention of the honeycomb structure described above. In this case, the adhesive layer includes a plurality of layers. It is also preferable to apply two or more adhesives having different compositions in two or more portions. In this way, when the adhesive layer is composed of a plurality of layers, for example, an adhesive is used so that the composition of the adhesive layer in contact with the honeycomb segment is close to the composition of the honeycomb segment, and the composition of the adhesive layer changes in a gradient manner. It is also preferable to use such an adhesive. Further, depending on the type of adhesive, a stronger adhesive force can be obtained by further drying and / or firing.
Another preferred method for bonding and integrating the honeycomb segments is, for example, as shown in FIG. 7, forming a spacer 10 on the bonding surface 7 of the honeycomb segment 12, and bonding to the bonding surface 7 as shown in FIG. This is a method including a step of applying the agent 13 and a step of bonding two or more honeycomb segments 12 as shown in FIG.
The step of forming the spacer 10 is a step of fixing the spacer on the adhesive surface 7. For example, a predetermined amount of a spacer forming agent is disposed at a predetermined position where the spacer is to be formed, and the spacer is formed by heating or drying. It can be fixed on the adhesive surface 7. The spacer forming agent is preferably fluid, and after the fluid spacer forming agent is disposed at a predetermined position, it is preferably solidified and fixed on the adhesive surface. As a method of disposing the spacer forming agent at a predetermined position, for example, a method of disposing a predetermined amount at a predetermined position on the adhesive surface using a pump capable of discharging a predetermined amount is preferable. As a method of forming the spacer by fixing the arranged spacer forming agent on the adhesive surface 7, a method of fixing the spacer forming material by heating or drying is preferable. For this purpose, various commonly used heating methods are used. An apparatus, a drying apparatus, or a heating / drying apparatus can be used. Here, it is preferable to heat and / or dry the spacer forming agent while applying pressure so that the spacer has a predetermined thickness.
As an example of a method of solidifying the spacer on the adhesive surface and fixing it on the adhesive surface, an example using the hot plate 16 is shown in FIG. In FIG. 10, a plate 15 having a predetermined thickness, for example, 0.5 mm, is disposed on the hot plate 16, and the portion of the adhesive surface on which the spacer forming agent 17 is disposed is the portion other than the portion on which the spacer forming agent is disposed. By contacting on the plate 15, the spacer forming agent 17 is heated while being pressurized with a hot plate so as to become a spacer having a thickness of 0.5 mm. In this case, the honeycomb segment may be pressurized by the dead weight of the honeycomb segment, or by the dead weight of the hot plate when upside down, or may be pressurized by using a pressure device. By such a method, a spacer having a predetermined thickness can be formed without variation.
The spacer forming agent is preferably a slurry containing ceramics, and further preferably contains a component common to the constituent components of the honeycomb segment. For example, it is preferable to add ceramic fiber or other inorganic fibers, organic / inorganic binders, and a dispersion medium such as water to ceramic powder common to the constituents of the honeycomb segment, and further use a sol-like substance such as Si sol. It is also preferable to include.
The spacer forming agent may be disposed on either one of the two adhesive surfaces facing each other with the adhesive layer interposed therebetween, but may be disposed on both. There are no particular restrictions on the amount, arrangement position, and number of arrangement of the spacer forming agent, and the amount of the desired thickness can be appropriately arranged in a balanced manner so that the thickness of the adhesive layer is uniform by the method described above. . In some cases, a base agent may be applied to the adhesive surface by spraying before placing the spacer forming agent. By applying the base agent, the adhesive strength between the spacer and the bonding surface can be improved. However, the base agent does not bond the honeycomb segments to each other.
The step of applying the adhesive to the adhesive surface is performed by applying the adhesive to one or both of the adhesive surfaces, as described above. In this case, it may be applied to an adhesive surface on which a spacer is formed, or may be applied to an adhesive surface on which a spacer is not formed, or both. Like the spacer forming agent, the adhesive is preferably a slurry containing ceramics. For example, an inorganic fiber such as a ceramic fiber, an organic / inorganic binder, and a dispersion medium such as water are mixed with ceramic powder common to the constituent components of the honeycomb segment. Those added are preferable, and it is also preferable to contain a sol-like substance such as Si sol. Further, it is preferable that the main component of the adhesive and the main component of the spacer forming agent are the same, that is, 50% by mass or more of the constituent components of the adhesive and the spacer forming agent are the same component. However, the shape such as the particle diameter may be different. Further, it is preferable that 70% by mass or more, particularly 90% by mass or more, is the same component from the viewpoint of enhancing adhesiveness and making defects difficult. Furthermore, it is preferable that the adhesive and the spacer forming agent are such that the constituents of the adhesive and the spacer to be formed are substantially the same.
The two or more honeycomb segments thus formed with spacers and coated with the adhesive are bonded in the same manner as described above, preferably while pressing, and preferably dried and / or heated to thereby provide two or more honeycomb segments. Can be bonded and integrated, and a honeycomb structure can be manufactured. There is no limit to the pressing force at this time, but 0.3 to 3 kgf / cm 2 It is preferable to press at a pressure of about 0.5-2 kgf / cm. 2 It is preferable to press at a certain pressure.
By manufacturing the honeycomb structure by such a method, the positional deviation of the spacer can be suppressed. In addition, when the spacer and the adhesive are made of ceramics and the main components are the same, it is not necessary to prepare a spacer in advance, and the above process can be automated as a series of processes, which can be suitably applied to mass production. There are also advantages.
In addition, when the honeycomb structure 1 manufactured according to the present invention is used for a filter, particularly a DPF or the like, it is preferable that the openings of the flow holes 3 are alternately plugged with a sealing material, and the end surfaces are alternately alternated. It is preferable to plug in a zigzag pattern. Plugging with the plugging material can be performed by masking the flow holes not plugged, applying the raw material to the opening end face of the honeycomb segment as a slurry, and firing after drying. In this case, it is preferable to plug the honeycomb segment during the above-described manufacturing process of the honeycomb segment, that is, after forming the honeycomb segment and before firing. It can be done at any time later. The material of the plugging material to be used can be suitably selected from the group mentioned as the preferable raw material of the honeycomb segment, but it is preferable to use the same raw material as the raw material used for the honeycomb segment.
In the present invention, a catalyst may be supported on the honeycomb structure. This method may be a method commonly performed by those skilled in the art. For example, the catalyst can be supported by washing a catalyst slurry, drying and calcining. This step may be performed at any time after the honeycomb segment is formed.
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
(Examples and Comparative Examples)
Next, the present invention will be described in more detail based on examples.
(Manufacture of honeycomb segments)
Silicon carbide powder and silicon powder were used as raw materials, and methyl cellulose and hydroxypropoxyl methyl cellulose, a surfactant and water were added thereto to produce a plastic clay. The clay was extruded and dried with microwaves and hot air. Next, this was heated and degreased in an air atmosphere and fired to obtain a square columnar honeycomb segment having dimensions of 58 mm × 58 mm × 150 mm (height) as shown in FIG.
(Example 1)
Two honeycomb segments obtained by the above manufacturing process, two sides of cardboard with dimensions of 50 mm × 10 mm × 0.8 mm (thickness) as spacers, SiC 40 mass%, silica sol 20 mass%, inorganic auxiliary 1 A ceramic adhesive comprising 10% by mass, 30% by mass ceramic fiber, and 9% by mass water is prepared. As shown in FIGS. 4 (a) and 4 (b), the side surface of the honeycomb segment, that is, the adhesive surface is made of ceramic. Adhesive was applied, and cardboards were placed in two places on the upper and lower sides of the side, pressed and bonded, and dried to obtain a honeycomb structure in which two honeycomb segments were integrated.
(Comparative Example 1)
A honeycomb structure was obtained in the same manner as in Example 1 except that the cardboard serving as the spacer was not used.
(Measurement of adhesive layer thickness)
For each of the honeycomb structures obtained in Example 1 and Comparative Example 1, the thickness of the adhesive layer at 10 measurement points 11 indicated by the numbers 1 to 10 circled on the adhesive surface 7 in FIG. Was measured. The measurement results are shown in Table 1.
Figure 0004155923
In the honeycomb structure obtained in Example 1, the thickness of the adhesive layer could be made substantially the thickness of the cardboard, that is, the desired thickness by interposing the cardboard as the spacer. Moreover, there was very little variation between the measurement points, and the thickness of the adhesive layer could be kept constant.
(Example 2)
Two honeycomb segments obtained as a result of the above manufacturing process, having a size of 10 mm × 10 mm × 0.8 mm (thickness) as spacers, SiC 43% by mass, silica sol 23% by mass, inorganic auxiliary agent 2% by mass, ceramic fiber 32% by mass 4% of an inorganic material composed of 4%, and an adhesive made of ceramics composed of 40% by mass of SiC, 20% by mass of silica sol, 1% by mass of inorganic auxiliary, 30% by mass of ceramic fiber, and 9% by mass of water. 5 (a) and 5 (b), a ceramic adhesive is applied to the side surface of the honeycomb segment, that is, the adhesive surface, and the inorganic material is disposed at four locations above and below the side surface and pressed. By bonding and drying, a honeycomb structure in which two honeycomb segments were integrated was obtained.
(Comparative Example 2)
A honeycomb structure was obtained in the same manner as in Example 2 except that the inorganic material as the spacer was not used.
(Measurement of adhesive layer thickness)
For each of the honeycomb structures obtained in Example 2 and Comparative Example 2, the thickness of the adhesive layer at 10 measurement points 11 indicated by numbers 1 to 10 surrounded by a circle on the adhesive surface 7 in FIG. Was measured. The measurement results are shown in Table 2.
Figure 0004155923
In the honeycomb structure obtained in Example 2, an inorganic material as a spacer was interposed, so that the thickness of the adhesive layer could be almost the thickness of the inorganic material, that is, the desired thickness. Moreover, there was very little variation between the measurement points, and the thickness of the adhesive layer could be kept constant.
(Example 3)
Twenty honeycomb segments obtained by the manufacture of the honeycomb segment were prepared, and the adhesive used in Example 2 was used as a spacer forming agent and arranged at four locations near the four corners of the bonding surface using a fixed supply pump. After that, as shown in FIG. 10, it is placed on a hot plate provided with an iron plate having a thickness of 0.5 mm, and solidified by heating at about 160 ° C. for about 6 seconds. As shown in FIG. Four spacers fixed on the adhesive surface were formed. When the thickness of this spacer was measured, it was within the range of 0.5 ± 0.1 mm.
Next, a predetermined amount as shown in FIG. 8 is applied to the surface of the honeycomb segment on which the spacer is formed, using the same spacer forming agent as the adhesive, and then a total of 16 honeycombs in 4 rows × 4 rows. Adhesive surfaces are bonded together to integrate the segments, and 1.0 kgf / cm 2 It pressed with the applied pressure. Next, the adhesive protruding from the adhesive surface was removed and dried to obtain a honeycomb structure.
(Comparative Example 3)
A honeycomb structure was obtained in the same manner as in Example 3 except that the inorganic material as the spacer was not used.
(Measurement of adhesive layer thickness)
For each of the honeycomb structures obtained in Example 3 and Comparative Example 3, the thickness of the adhesive layer at 10 measurement points 11 indicated by the numbers 1 to 10 circled on the adhesive surface 7 in FIG. Was measured. Table 3 shows the measurement results. In the honeycomb structure obtained in Example 3, the thickness of the adhesive layer could be kept constant at a predetermined thickness with little variation between measurement points by interposing an inorganic material as a spacer.
Figure 0004155923
Industrial applicability
In the honeycomb structure of the present invention, since the spacers are arranged between the honeycomb segments, the thickness of the adhesive layer between the honeycomb segments can be set to a desired thickness and uniform, thereby reducing the dimensional accuracy. A few honeycomb structures could be obtained. In addition, the honeycomb structure having the above effects could be easily made by the manufacturing method of the present invention. The honeycomb structure of the present invention can be suitably used for a catalyst carrier utilizing a catalytic action such as an internal combustion engine, a boiler, a chemical reaction device, and a fuel cell reformer, or a particulate collection filter in exhaust gas.
[Brief description of the drawings]
FIGS. 1A and 1B are schematic views showing an embodiment of a honeycomb structure according to the present invention, where FIG. 1A is a perspective view and FIG. 1B is a schematic plan view.
FIG. 2 is a schematic cross-sectional view showing another embodiment of the structure according to the present invention.
FIG. 3 is a schematic perspective view showing an embodiment of the honeycomb segment according to the present invention.
4 (a) and 4 (b) are schematic views in which spacers are arranged on the honeycomb segment according to the present invention, FIG. 4 (a) is a side view, and FIG. 4 (b) is a front view.
5 (a) and 5 (b) are other schematic views in which spacers are arranged on the honeycomb segment according to the present invention, FIG. 5 (a) is a side view, and FIG. 5 (b) is a front view.
FIG. 6 is an explanatory view showing the measurement points of the thickness of the adhesive layer on the side view of the honeycomb segments manufactured in Examples 1 to 3. FIG.
FIG. 7 is a diagram showing an example of the manufacturing method of the present invention, and is a schematic perspective view showing a state in which a spacer is formed on the bonding surface of the honeycomb segment.
FIG. 8 is a diagram showing an example of the manufacturing method of the present invention, and is a schematic perspective view showing a state in which an adhesive is applied to the bonding surface of the honeycomb segment.
FIG. 9 is a diagram showing an example of the manufacturing method of the present invention, and is a schematic perspective view showing a state in which honeycomb segments are bonded and integrated.
FIG. 10 is a diagram showing an example of the manufacturing method of the present invention, and is a schematic perspective view showing a state in which the spacer forming agent disposed on the bonding surface of the honeycomb segment is heated.

Claims (2)

隔壁により仕切られた軸方向に貫通する多数の流通孔を有するハニカムセグメントを製造する工程、及び複数の前記ハニカムセグメントを接着一体化する工程を備えるハニカム構造体の製造方法であって、A method for manufacturing a honeycomb structure including a step of manufacturing a honeycomb segment having a large number of flow holes penetrating in the axial direction partitioned by partition walls, and a step of bonding and integrating the plurality of honeycomb segments,
前記ハニカムセグメントを接着一体化する工程において、スペーサーを接着面に介在させ、In the step of bonding and integrating the honeycomb segments, a spacer is interposed on the bonding surface,
前記ハニカムセグメントを接着一体化する工程が、ハニカムセグメントの接着面にスペーサーを形成する工程、ハニカムセグメントの接着面に接着剤を施与する工程、及びハニカムセグメントを接着する工程を含み、The step of bonding and integrating the honeycomb segments includes a step of forming a spacer on the bonding surface of the honeycomb segment, a step of applying an adhesive to the bonding surface of the honeycomb segment, and a step of bonding the honeycomb segment,
前記接着剤の主成分と、前記スペーサー形成剤の主成分が、同一であるハニカム構造体の製造方法。A method for manufacturing a honeycomb structure, wherein the main component of the adhesive and the main component of the spacer forming agent are the same. 前記スペーサーをハニカムセグメントの接着面に形成する工程が、前記接着面上に流動性のスペーサー形成剤を配置し、これを固化させることにより行われる請求項１に記載のハニカム構造体の製造方法。The method for manufacturing a honeycomb structure according to claim 1, wherein the step of forming the spacer on the bonding surface of the honeycomb segment is performed by disposing a fluid spacer forming agent on the bonding surface and solidifying it.
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Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL205740B1 (en) * 2001-12-06 2010-05-31 Ngk Insulators Ltd Honeycomb structure body and method for manufacturing the same
JP4455818B2 (en) 2003-01-14 2010-04-21 日本碍子株式会社 Ceramic honeycomb structure and manufacturing method thereof
JP4267947B2 (en) * 2003-03-19 2009-05-27 日本碍子株式会社 Honeycomb structure
JP4476557B2 (en) * 2003-03-25 2010-06-09 日本碍子株式会社 Joining method of ceramic structures
WO2005047210A1 (en) 2003-11-12 2005-05-26 Ibiden Co., Ltd. Ceramic structure body, device for producing ceramic structure body, and method for producing ceramic structure body
US20090288380A1 (en) * 2004-07-12 2009-11-26 Vincent Gleize Filtration structure, in particular a particulate filter for the exhaust gases of an internal combustion engine, and associated exhaust line
CN100534617C (en) 2005-06-24 2009-09-02 揖斐电株式会社 Honeycomb structure body
JPWO2006137158A1 (en) * 2005-06-24 2009-01-08 イビデン株式会社 Honeycomb structure
CN101023044B (en) * 2005-06-24 2010-04-21 揖斐电株式会社 Honeycomb structure body
WO2006137156A1 (en) * 2005-06-24 2006-12-28 Ibiden Co., Ltd. Honeycomb structure body
CN101001698B (en) 2005-06-24 2011-02-09 揖斐电株式会社 Honeycomb structure body
WO2006137150A1 (en) 2005-06-24 2006-12-28 Ibiden Co., Ltd. Honeycomb structure body
WO2006137155A1 (en) * 2005-06-24 2006-12-28 Ibiden Co., Ltd. Honeycomb structure body
JP5031562B2 (en) * 2005-06-24 2012-09-19 イビデン株式会社 Honeycomb structure
AT502666B8 (en) 2005-12-16 2007-07-15 Porzellanfabrik Frauenthal Gmb METHOD AND WAVE BODY FOR CLEANING AND / OR REGENERATING GASES
WO2008105082A1 (en) * 2007-02-28 2008-09-04 Ibiden Co., Ltd. Honeycomb structure
JP5430867B2 (en) * 2007-06-21 2014-03-05 イビデン株式会社 Honeycomb structure and method for manufacturing honeycomb structure
WO2008155856A1 (en) * 2007-06-21 2008-12-24 Ibiden Co., Ltd. Honeycomb structure and process for producing the same
JP5513895B2 (en) 2007-11-28 2014-06-04 日本碍子株式会社 Method for joining plugged honeycomb structures
JP5242178B2 (en) * 2008-01-17 2013-07-24 日本碍子株式会社 Honeycomb segment with spacer and honeycomb structure
WO2009118813A1 (en) * 2008-03-24 2009-10-01 イビデン株式会社 Honeycomb structure and process for producing the same
WO2011051901A1 (en) 2009-10-28 2011-05-05 Saint-Gobain Centre De Recherches Et D'etudes Europeen Assembled filter body having variable specific thermal resistance
WO2011121712A1 (en) * 2010-03-29 2011-10-06 イビデン株式会社 Honeycomb structure and process for production of honeycomb structure
FR2965489B1 (en) 2010-09-30 2013-03-29 Saint Gobain Ct Recherches FRAME STRUCTURE OF MICROFINED BEES.
JP2012076931A (en) * 2010-09-30 2012-04-19 Tokyo Yogyo Co Ltd Honeycomb structure
CN104364224B (en) 2012-06-28 2018-07-20 陶氏环球技术有限责任公司 The method of array for bonded ceramics filter
JP6285234B2 (en) 2014-03-25 2018-02-28 日本碍子株式会社 Manufacturing method of honeycomb structure
WO2016159063A1 (en) 2015-03-31 2016-10-06 日本碍子株式会社 Method for manufacturing honeycomb structure and binder

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2003A (en) * 1841-03-12 Improvement in horizontal windivhlls
US4335783A (en) * 1980-11-10 1982-06-22 Corning Glass Works Method for improving thermal shock resistance of honeycombed structures formed from joined cellular segments
JPS6126572A (en) * 1984-07-16 1986-02-05 株式会社日本自動車部品総合研究所 Ceramic product and manufacture
JPH0193473A (en) * 1987-10-01 1989-04-12 Sumitomo Chem Co Ltd Production of formed ceramic article having honeycomb layer on surface
JPH01192536A (en) * 1988-01-27 1989-08-02 Ube Ind Ltd Honeycomb core made of polyimide and preparation thereof
US5104627A (en) * 1988-12-19 1992-04-14 Usui Kokusai Sangyo Kabushiki Kaisha Exhaust gas cleaning apparatus
JPH04130069A (en) * 1990-09-19 1992-05-01 Matsushita Electric Ind Co Ltd Manufacture of honeycomb-type ceramic structure
JP3192683B2 (en) * 1991-06-15 2001-07-30 住友大阪セメント株式会社 Ceramic material joining method
US5678968A (en) * 1995-07-03 1997-10-21 Hexacomb Corporation Honeycomb roll spacer
DK1306358T4 (en) * 1996-01-12 2012-10-22 Ibiden Co Ltd sealing
JPH09192453A (en) * 1996-01-19 1997-07-29 Ngk Insulators Ltd Catalytic convertor
JP3971027B2 (en) * 1998-06-25 2007-09-05 イビデン株式会社 Ceramic structure bonding apparatus and bonding method
JP3862458B2 (en) * 1999-11-15 2006-12-27 日本碍子株式会社 Honeycomb structure
JP3889194B2 (en) * 2000-01-13 2007-03-07 日本碍子株式会社 Honeycomb structure
JP4368050B2 (en) * 2000-09-27 2009-11-18 イビデン株式会社 Manufacturing method of ceramic structure
JP4404497B2 (en) * 2001-03-01 2010-01-27 日本碍子株式会社 Honeycomb filter and manufacturing method thereof

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